Copper-containing azo dyestuffs



United States Patent Oihce 2,745,828 Patented May 15, 1956COPPER-CONTAINING AZO DYESTUFFS Ernst Iselin, Dornach, and WalterWehrli, Riehen, Switzerland, assignors to Sandoz A. G., Basel,Switzerland, 2 Swiss No Drawing. Application July 2, 1953, Serial No.365,773

Claims priority, application Switzerland July 9, 1952 8 Claims. (Cl.260-146) SOQH wherein R has the precedingly-recited significance, and R1stands for a radical of the benzene or naphthalene series, and with onemol of an azo component containing the enolizable grouping CO-CH2,treating the resultant azo dyestufi with an acid agent in order to formthe azine ring, and then treating with a copper-yielding agent in orderto effect conversion into the copper complex compound.

. The new dyestuifs are dark powders which, in concentrated sulfuricacid give a characteristic solution coloration, and which dye cotton andfibers of regenerated cellulose predominantly in neutral gray shades ofexcellent fastness to light and good fastness to washing and toperspiration. They correspond to the formula I OQu 0 ou-o-o- SOJH N\ILwherein R has the aforesaid significance, and wherein the enolizedgrouping constitutes a part of the radical of a corresponding azocompound. 4

3,3-dialkoXy-4,4'-diamino-l,1'-diphenyls, which are suitable for thepreparation of the tetrazo compounds are preferably3,3'-dimethoxy-4,4-diamino-l,1'-diphenyl and 3 ,3'-diethoxy4,4'-diamino-l, l -diphenyl.

Illustrative of the azines of Formula I are for example the following:

5-hydroxy-1,2-naphthophenazine-7-su1fonic acid,

5 hydroxy 4' methyl l,2,1,2' naphthophenazine- 7-sulfonic acid,

5 hydroxy 5' methyl 1,2,1',2' naphthophenazine- 7-sulfonic acid,

5 hydroxy 4 methoxy l,2,1',2' naphthophenazine- 7-sulfonic acid,

5 hydroxy 5' methoxy l,2,1',2' naphthophenazine- 7-sulfonic acid,

5 hydroxy 4' chloro 1,2,1,2' naphthophenazine- 7-sulfonic acid,

5 hydroxy 5' chloro l,2,1',2' naphthophenazine- 7-sulfom'c acid,

5 hydroxy 4 carboxy l,2,1',2 naphthop'henazine- 7-su1fonic acid,

5 hydroxy 5' carboxy l,2,1,2 naphthophenazi'ne- 7-sulfonic acid,

5 hydroxy 4 hydroxy 5' carboxy l,2,1',2' naphthophenazine-7-sulfonicacid,

5 hydroxy 4 carboxy 5' hydroxy 1,2,l',2' naphthophenazine-7-sulfonicacid,

5 hydroxy l,2,1,2' naphthophenazine 4',7 disulfonic acid,

5 hydroxy 1,2,1',2' naphthophenazine -5',7 disulfonic acid,

5,5 dihydroxy 1,2,2,l' dinaphthazine 7,7 disulfonic acid, etc.

The azines are preferably prepared from or'thoarylaminoazo compounds bytreatment with acids (see H. E. Fierz-David, Kiinstliche organischeFar'bsto'fie, Berlin, Julius Springer, 1926, page 309). If the azinesare made starting from meta-substituted arylaminoazo compounds, itappears for steric reasons that the position para to the substituent isinvolved in the ring closure, so that the meta-substituent is in the5-position.

Other azines which may be used in preparing the dyestuffs according tothe present invention comprise inter alia the5,5'-dihydroXy-l,2,l',2'-dinaphthaZine-7,7'-disulfonic acid, obtained bythe oxidation of 2-aniino-5-hydroxynaphthalene-7-sulfonic acid withhypochlorite solution (Javelle water) and the -hydroxy-l,2,9,l0'-naphthophenanthrazine-7-sulfonic' acid, which can be prepared bycondensation of 1,2-diamino-5-hydroxynaphthalene-7- sulfonic acid with9,IO-phenanthrenequinone.

Monoazo compounds of Formula II which can be employed in preparing theazo intermediates and in which an azine ring is then formed, comprisefor example:

5 hydroxy 2 phenyl i aminonaphthalene -,1,1 azobenzene-4,7-disulfonicacid, 5 hydroxy 2 phenyl aminonaphthalene 1,1 azobenzene-3,7-d.isulfonic acid,

5 hydroxy 2 (4" methyl) phenylaminonaphthalene-1,1'-azobenzene-4',7-disu1fonic acid, 5 hydroxy 2 (3"methyl) phenyl aminonaphthalene-l,1-azobenzene-4,7-disulfonic acid,

5 hydroxy 2 (4" methoxy) phenylaminonaphthalene-1,l-azobenzene-4,7-disulfonic acid, 1 5 hydroxy 2 (4"chloro) phenyl aminonaphthalene-1,1-azobenzene-4,7-disulfonic acid,

5 hydroxy 2 (3" chloro) phenyl aminonaphthalene l,1'-azobenzene-3 ',7disulfonic acid,

5 hydroxy 2'- (3" carboxy) phenylaminonaPhthalene-l,l'-azobenzene-7-sulfonic acid,

5 hydroxy 2 (4 carboxy) phenylaminonaphthalene-l,l-azobenzene-7=sulfonic acid,

5 hydr oxy 5 2 (4" hydroxy 5" carboxy)phenylaminonaphthalene-l,l'-azobenzene-7-sulfonic acid,

5 hydroxy 2 (4" carboxy 5" hydroxy)phenylaminonaphthalene-l,1-azobenzene-7-sulfonic acid,

5 hydroxy 2 phenyl aminonaphthalene 1,1 azobenzene-4",7-disulfonic acid,

5,- hydroxy 2 phenyl aminonaphthalene 1,1 azobenzene-3",7-disulfonicacid,

5,5 dihydroxy 2,2 dinaphthylamine 1, l azobenzene-7, 7 "-disulfonicacid, 7 5,5 diliydroxy 2,2 dinaphthylamine 1, 1azobenzene-4",7,7-trisu1fonic acid, etc.

1-acetoacetylaminobenzene-4-sulfonic acid, 1acetoacetylaminobenzene-3-sulfonic acid,l-acetoacetylaminobenzene-4-carboxylic acid, i.1-acetoacetylaminobenzene-3-carboxylic acid,1-acetoacetylamino-4-hydroxyb enzene-3carboxylic acid,1-acetoacetylamino 3-hydroxybenzene-4-carb0xylic acid,

lacetoacetylamino-Z-methoxybenzne-4-sulfonic acid,

1-acetoacetylaminonaphthalen'e-3,6-disulfonic acid,1eacetoacetylaminonaphthalene-3,g-disulfonic acid,1-acetoacetylaminonaphthalene4,8-disulfonic acid;Lacetoacetylaminonaphthalene-4,S-disulfonic' acid,2-acetoacetylaminonaphthalene-S,7-disulfonic acid,.Z-acetoacetylarninonaphthalene-6,8-disulfonic acid,4-acetoacety1amino-1,1-azohenzene-4 sulfonic acid, The acetoacetic acidamides of dehydrothio ptoluidinemonoand -di-sulfonic acids, etc.

Suitable 5-pyrazolones for the purposes of the present inventioncomprise inter alia:

1-phenyl-3-methyl-5-pyrazolone-3-sulfonic acid,1phenyl-3-methyl-5-pyrazolone-4-sulfonic acid,1-phenyl-S-inethyl-S-pyrazolone-3-carboxylic acid,1-phenyl-3-methyl-5-pyrazolone-4-carboxylic acid,1-phenyl-3-methyl-5-pyrazolone-2,5-disulonic acid,1phenyl-3-carboxy-5-pyrazolone-3'-sulf0nic acid,1:phenyl-3-carboxy-5-pyrazolone-4-sultonic acid,1phenyl-3-methyl-5-pyrazolone-3-sulfonic acid amide,1-pheny1-5-pyrazolone-3-carboxylic acid amide,

. ti 1-phenyl-3-carboxy-5-pyrazolone-3'-sulfonic acid amide, 1 (2',5dichloro) phenyl -3 methyl -'5 pyrazolone- 4'-sulfonic acid,1-(1'-naphthyl)-3-methyl-5-pyrazolone-4sulfonic acid, 1( 1'-naphthyl) -3-methyl-5-pyrazolone-5-sulfonic acid, 1-( 1-naphthyl)-3-methyl-5-pyrazolone-6-sulfonic acid, 1-( 1'-naphthyl)-3-methyl-5-pyrazolone-7'-sulfonic acid, 1-1'-naphthyl)-3-methy1-5-pyraZolone-8-sulfonic acid,1-(2'-naphthyl)-3-methyl-5-pyrazolone-l-sulfonic acid, 1-(2-naphthyl)-3-methyl 5-pyrazolone-5-sulfonic acid, 1-(2-naphthyl)-3-methyl-5-pyrazolone-6-su1fonic acid, 1- (2'-naphthyl)-3-methyl-,5-pyr azolone-8'-sulfonic acid, 1 (1' naphthyl) 3 methyl 5pyrazolone; 3L6- disulfonic acid, W 1 (1 naphthyl) 3 methyl 5 pyrazolone3',8'-

disulfoniciacid, a

1 (1 naphthyl) 3 methyl d pyraz olone 4,8-

disulfonic acid, a 7 a V W 1 (2' naphthyl) 3 methyl 5 pyrazolone 3",6-

disulfonic acid,

1 (2 naphthyl) 3 methyl 5 pyrazolone 4,8-

disulfonic acid,

1 (2 naphthyl) 3 methyl 5 pyrazolone 5,7- disulfonic acid,

1 (2' naphthyl) 3 methyl 5 pyrazolone 6,8'-

disulfonic acid,etc.

The coupling of the tetrazo compounds of the3,3'-dialkoxy-4,4-diamino-1,1-diphenyl with the azine (I) or the monoazocompounds (II) and the azo component containing the enolizable groupingCO-CHz-, can be carried out, according to the invention, in any suitableorder of succession. If in the thus-obtained azo dyestufis it is stillnecessary to form the azine ring, this is effected for example bydissolving and stirring the azo dyestuff in concentrated sulfuric acidor phosphoric acid at room temperature or by heating in dilute mineralacid to 80-100C.

The conversion of the azine ring-containing azo dyestuffs into thecopper complex compounds is carried out with splitting of the3,3-dialkoxy groups of the diphenyl radical. A particularly smoothconversion is obtained when the said splitting is efiected by heatingthe dyestuff at or near the boiling temperature in an aqueous solutionin the presence of the copper tetrammine complex compounds obtained fromcopper sulfate and ammonia, the splitting being carried out if desiredin the presence of an organic base, or by heating in a melt preparedfrom copper .sulfate'and an alkali metal salt of 'a low molecularaliphatic monocarboxylic acid.

The following examples illustraterepresentative embodiments of theinvention but are not intended to be limitative. In these examples theparts and percentages are by weight, and the temperatures are in degreescentigrade.

Example 1 24.4 parts of 4,4-diamino-3,3'-dirnethoxy-1,1-diphenyl aretetrazotized and, while cooling with ice are coupled with 32.6 parts ofS-hydroxy-1,2-napthophenazine-7-snlfonic acid in the presence of sodiumcarbonate.

The resultant intermediate is precipitated by the addition of sodiumchloride to the coupling solution and is filtered off. The thus-obtainedconcentrated paste is introduced, at a temperature of 010, into asolution of 42.8 parts of the sodium salt of 1-(2-naphthyl)-3-methy1-5-pyrazolone-6,8-disulfonic acid, 200 parts of water and 100 parts ofpyridine base mixture. Upon completion of the second coupling, thedyestufi is isolated, stirred into 1800 parts of water and, after theaddition of 20 parts of sodium carbonate and 500 parts of an ammoniacalcopper oxide solution which contains 50 parts of crystalline coppersulfate and parts of concentrated aqueous ammonia solution, theresultant solution is heated to boiling under reflux for 6 to 12 hours.The thus-obtained copper complex compound is precipitated, filtered ofland dried. It is a dark powder, which corresponds to the formula OCu 0 0dissolves with reddish blue coloration in water and gray coloration incencentrated sulfuric acid and dyes cotton and fibers of regeneratedcellulose in beautiful neutral gray shades of good fastness to light, toWashing and to perspiration.

The identical dyestuff is obtained when, in the fore: going, the 24.4parts of 4,4-diamino-3,3-dimethoxyl,1-diphenyl are replaced by 27.2parts of 4,4'-diamino- 3,3-diethoxy-l,1'-diphenyl.

Example 2 24.4 parts of 4,4-diamino-3,3' dimethoxy-hl'-di phenyl aretetrazotized and, while cooling with ice, are coupled in the presence ofsodium carbonate with 54.3 parts of the sodium salt of the monoazodyestuff obtained by the acid coupling of diazotized l-aminobenzene-4-sulfonic acid with 2-phenylamino-S-hydroxynaphthalene-7-sulfonic acid.The resultant intermediate is precipitated by the addition of sodiumchloride to the coupling solution and is then filtered oif. The wellpressed filter cake is introduced into the solution of 42.8 partsof thesodium salt of 1-(2'-naphthyl)-3-methyl-5-pyrazolone-6,8'-disulfonicacid in 200 parts of Water and 100 parts of pyridine base mixture. Uponconclusion of the coupling, the reaction product is separated and inorder to produce an azine ring, is introduced into concentrated sulfuricacid, the resultant solution being stirred for 6 to 12 hours at roomtemperature (-30"). Upon conclusion of the azine ring formation, thesolution is poured into a mixture of ice and Water, and the new dyestuffisolated therefrom as alkali metal salt. For conversion thereof into thecopper complex compound, it is heated with a copper-yielding agent untilthe methoxy groups are split. The coppered dyestufl has the samecomposition and the same properties as the product described in Example1.

Example 3 24.4 parts of 4,4-diamino-3,3'-dimethoxy-1,l'-diphenyl aretetrazotized. For stabilization of the diazonium groups, 40 parts ofnaphthalene-Z-sulfonic acid are scat- '6 tered into the diazo solution.While cooling with ice, the tetrazo compound is coupled in the presenceof sosulfate and 20 parts of Water, the melt heated and Water distilledoff until the temperature of 170 is reached. Boiling is then continued,under reflux for 6 to 12 hours whereby the methoxy groups in thediphenyl radical are split and the disazo dyestuff is coppered. Water isthen added dropwise to the melt until all salts have dissolved but thedyestuff has not yet dissolved. The dyestufl is o o l l N=N thereuponfiltered oif and dried. The new copper-containing disazo dyestuff is ablack powder which corresponds to the formula Cu-O- t L-C ONH OgHdissolves with reddish gray coloration in water and with gray colorationin concentrated sulfuric acid and dyes cotton and fibers of regeneratedcellulose in neutral gray shades of good fastness to washing and tolight.

Example 4 24.4 parts of 4,4-diamino-3,3'-dimethoxy-1,1'-diphenyl aretetrazotized and, at a temperature of 0-5 and in presence of sodiumcarbonate, are coupled with 45 parts of the sodium salt of5-hydroxy-1,2,1',2-naphthophenazine-4',7-disulfonic acid in solution in600 parts of water. Upon completion of the resultant intermediateformation, the solution of 27.6 parts of the sodium salt oflphenyl-3-methyl-5-pyrazolone-3-sulfonic acid in 300 parts of water isrun in. The coupling can be accelerated by the addition of parts ofpyridine base mixture to the mass. The resultant disazo dyestuff issalted out and isolated. Conversion thereof into the copper complexcompounds can be effected, for instance according to one of the methodsdescribed in Examples 1 and 3. The new which dissolves with bluecoloration in water and in concentrated sulfuric acid and which dyescotton and fibers OzH dissolves with reddish blue coloration in waterand with blue. coloration in concentrated sulfuric acid and dyes ofregenerated cellulose in neutral gray shades with good fastness tolight, washing and perspiration.

The following table sets forth examples of additional cotton a fibers fregenerated cellulose in p y y dyestufis, which can be obtained bycoupling'l mol shades with very good fastness to light, to washing andAB to perspiration.

a Dyeing of Azo component con- Example Alma taming the enollz- 23 5 1 P9X N0. able grouping compound C on cotton 65-hydroxy-3-chlorol-phenyl-B-methyl-S- Gray.

1 2,1',2'-naphthopyrazolone-2,5'- phlecalnazinefl-sulfonic disulfonicacid. 8.0 7 5-hydr0xy-4'-carboxy- 1-phenyl-3-methyl-5- Blue-gray.

- 1,2,1,2-naphthopyrazolone.

phenazine-7-sulfonic 3G1 V 8 5,%-dihydr]o xy -5-cal-phenyl-f-meihylfi-Gray.

OXY-l 2 2 -nap PYIEZO one -S11 Example 5 thophe'nzizineflicnic acid.

sulfonic acid. To the aqueous solution of the intermediate from 24.4 95-hydroxy-4-chlor0 1-(2'-naphthyl)-3- Do.

I e I 1,2,1',2-naphthomethy1-5-pyraz0- parts of terazotized 4.4-d1am1no-3,3 -d1methoxy-l,l -d1- pne naztneq-sulfonic 10n;5,7-disulfonic301 301 4 1 an d d l0 5 5-d1hydroxy-1 2 l-acetoacetylamino- Do. pheny dp s of s 1m salt of 5 by KY 1,2,1 ,2 V igla ii fii j belzenedg sulfonicis onicaci. aci amt e. naphthophenazine 4,7 disulfomc acid, obtainedaccord 11 dr W13, 1 acet0acety1amm9 ing to the indications in Example4,,there is added a so- 1* 5 l fi g i fiflgiiffgigf- 1 g g if B1 N 2-2,1,2- n- -a. lution of 27.9 parts of the sodium salt ofl-acetoacetyla- 45 ngph fii tgmenazine- -c oxy li gid e ue gr y4,7-disu1tonic acid. mmobenzene-2-sulfon1c and m 400 parts of water. 135-hydroxy-1,2,1,2- 1-(3-sulfamido)- Do.

7 V naphthophenazi nephenyl-5-pyr azo1one- When the coupling is over,the reaction product is seps f0 deg y 01d 31111 e. arated, again stirredinto 2000 parts of Water and, after 14 U l'acetwcetylammfl' Gray- 41aggitslilziphqnaznehytllaroxsl'henfine-ft- 01110 2.01 C31 OXY 10 ac theaddition of 25 parts of sodium carbonate and 500 15 he l acetoacetylamm9D0 parts of ammoniacal copper oxide solution which con- E53? carboxyhel6 6-11 drox -4-amlnodo Do. tams 50 parts of crystalline sulfate and 85parts of connaphthophenazinecentrated aqueous ammoma solution, heated tobOlllIlg 5o 7-sulionic acid.

17 do 1-phenyl-3-methyl-5- Blue-gray. under reflux for 6 to 10 hours.The copper-containing ggggggig 18 5-hydroxy-4-amino- 1-phenyl-3-methyl-5- Do. dlSflZO dyestuff, thus produced, 18 precipitated, filteredoif g i g y gymzolgneahsub p EH32 ne- 01110801 and dried. It is a darkpowder which corresponds to the dismfomc mm formula u 0 1 i l I N=N NSOsH to the formula 1. I

0 0 ou-o-oof tetrazotized 3,3-dimethoxy-4,4'-diamino-1,1-diphenyl 9 H II with one mol of an azine and one mol of an azo com- GC ponentcontaining the enolizable COCH2 group- 8 ing, followed by coppering,essentially in accordance with the indications in the precedingexamples. L

The dystuft' of Example 6, for instance, corresponds 10 to the formula Rwherein R stands for a radical selected from the group smH / SOJHExample 19 3 0.1 part of any of the dyestuifs disclosed in the precedingexamples is dissolved in 300 parts of water at 50. 0C- 10 parts ofcotton are entered into the dyeing bath; the latter is heated to 95 inthe course of to 20 minutes and maintained at this temperature forminutes. In 5 forms a part of the radical of an azo compound selectedthe course of the dyeing process, 1 to 4 parts of Glauber from the groupconsisting of the l-aryl-S-pyrazolone and salt are added portionwise inthe form of a 10% aqueous acetoacetylaminoaryl series. solution. Thedyebath is then allowed to cool to 2. Copper-containing azo dyestufiswhich correspond the dyed material withdrawn, rinsed and dried. Dependtothe formula consisting of the benzene and naphthalene series, andwherein the grouping ing upon the dyestufi employed, the product will bea blue-gray to gray dyeing of good fastness to light, to washing and toperspiration.

Fibers of regenerated cellulose are dyed in the same wherein each of theRs stands for a radical selected from the group consisting of thebenezene and naphthalene 1. Copper-containing azo dyestuffs whichcorrespond series.

Having thus disclosed the invention, what is claimed is- '11 4. Thedyestuffs which correspond to theformfila 5. The dyestufis whichcorrespond to the formula OCu m N CH3 6. The dyestuffs which correspondto the formula 7. The. dyestufis which correspond to the formula52,?45328 I 13 14 8. The dyestuffs which correspond to the formulaReferences Cited in the file of this patent UNITED STATES PATENTS1,873,628 Ohlendorf Aug. 23, 1932 2,529,527 Wehrli et a1. Nov. 14, 19502,598,126 Iselin et a1 May 27, 1952

1. COPPER-CONTAINING AZO DYESTUFFS WHICH CORRESPOND TO THE FORMULA